Dyesttjffs of the thiazene series



Patented Apr. 9, 1935 Richard 'Herz, 'Frankfort-onthe- MainQ 7 Werner Zerweck and Wilhelm ,Hechtenberg;

Frankfort on the Main Fechenheim,

Ger

many, assignors to General Aniline Works, Inc.,

New York,'N; Y., .a'corporation of Delawarev l N Drawing. Application October 27, 1932, Serial No. 639,928. In Germany November 4, 1981 Our present invention relates to dyestuffs of the thiazine series described in U. S. Patent 1,588,384.

In said patent and British Patent No. 265,641 quinone vat dyestufis are described, which correspond tothe generalformula:

in which R1 indicates aryl, Rihydrogen, alkyl or aralkyl, X hydrogen or a monovalent substituent and; Y hydrogen or. a. monovalentz-substituent, particularly halogen (chlorine) which dyestufis 2 0. dye particularly animalfibers in the vat and are capable in a surprising manner of being fixed on vegetable fibers according-to the methods usual for dyestuffs containing sulfur.

However, the case of some members of :this

the moleculeof which the attached aryl-radicle signified by R1 in the above formula; is a higher molecular complex (i. e. contains several substituents or more "than one benzene-nucleus); often some difficulties arise when the dyestufis are applied for1machine dyeing in apparatus or dyein in the iece-i. The e: difficul n a b involved owingto the fact that these dyestuffs incline to separate from the dye-bath in a crystallme rm .sqfi t, une e dr ir earns e.

obtained; y

In accordance with our present invention this disadvantage can be entirely corrected andgderivatives of the quinone vat dyestuffs of the aforesaid type are obtainable, which are easily soluble in the sodium sulfide bath at all practical concentrations, and temperatures when into the molecule of the; said-dyestuffsis-int'ro'duced the group -SO2NH, either the sulfur or themaforesai aryl-radiclesignified ,by 3R1,

seriesjof'idyestuifs, namelyofzsuch .dyestufis, in

trogen atom of this group tbeing attachedfito "the The new dyestuffs correspond probably to'th'e 7 general formula:

wherein R and R1 indicate an aryl radicle of the benzene, diphenyl or naphthaleneseries,.Xthy 15 drogenor amonovalent substituent and Y hydrogen orghalogen.

Itis a remarkable fact, that by the introducetion of p the group -SOz-:-NI-Ie -the excellent affinityjof thepresent' dyestuff class forthe vege- Y 20;,

table fibers is not'diminished. The dyeings obtainedby means ofthe new derivatives are disa tinguished by a particular brightness of shade combined fastness properties which are sufiicienttosatisfy practical demand. The pres- '25:

ent inventiontherefore constitutes animportant technical advance; '1

The manufacture of the newderivatives of *thequinone vat dyestuffs maybe carried'out'for example from starting materials corresponding 30 torthose of UaS. Patent 1,588,384 and prepared by condensing thev arylenethiazthionium chlorides-with aromatic compounds containing in the molecule in addition to the primary or secondary amino group at least one SO2-NH group.

murder to further illustrate our invention the following example is given, the parts being by weight; but it-isnhderstood that our invention is not limited to,the particular products nor reacting conditions mentioned" therein:

Example 52.6 parts of 3-methyl-5 (p'-phenylamino-' probable formula:

sulfo diphenyl) 2.1 aminothiophenol of the is weakly acidified and the separated dyestufi is filtered ofi and washed. The dyestufi, which corresponds to the probable formula:

It is easily soluble in the sodium sulfide bath from which cotton is dyed bright greenish blue shades.

The aminothiophenol compound employed as starting material may be prepared as follows:-

3-methyl-5-chloro- 1.2 -phenylenethiaz-thionium chloride is condensed with p aminodiphenyl-p'-sulfanilide in the presence of glacial acetic acid according to U. S. Patent 1,588,384. The 3 methyl 5 (p'-phenylamino sulfo diphenyl) amino 1.2 phenylenethiaz-thionium chloride thus formed separates as a thick pulp of crystals of a metallic lustre, which are filtered ofi, washed with a dilute salt silution to which some hydrochloric acid has been added, and dried. This product is then transformed into the zinc mercaptide of the corresponding aminothiophenol by saponification and precipitating the solution with a zinc chloride solution according to U. S. Patent. 1,588,384;

ilQ i i; Y

is when dry a bluish powder of metallic lustre which dissolves in nitrobenzene with a reddish blue, in sulfuric acid with a pure blue color.

In the following table the behavior of some further dyestuffs of this series is described:

Shade 0]; the gye- I C l I th 1 ingso taine on 001' o s so u- Oolor of the so? cotton with the tion in eoncen- Dyestufl of the probable formula dyesmfi from Hated Sulfuric tbleollllzenlell nitrothe sodium sulacid flde bath (3H1 G1 I I J Blue when cold s KI g f g Violet' Greenlsh-blueflu; violet when 2 warm.

'7 v t CH: c1

N 01 r Blue when cold, Violet-blue Blue-. reddishviolet v 111' S 0 A whenwarm. .QD-H o: c1

. (lJH: (ill I (I 01 o nibbl Bl Bl ree s 1.19..... no ue. OzS-HN N S O 3 0.

CH: (ill Greenish-blue-..;- Blue ig i g gf 'Z Dyestufi of the probable formula cotton with the 6211655655 Sam.

tion in concen- Color of the solution in vnitrodyestufl from trated sulfuric the sodium sulacid benzene 5 fide bath .Greenish 111m Blue gg g g P 7. Greeni sh blue-. .l I B1ue-... .i. Blue.

0 w Purereddishiblue. erm..-...; violecwhmwmh. -01 1 m; wheii' ciihi;

HN Reddish blu 181110.. {,Qfif when HN B O l mam b1ue..---- Blue Blues group hydrogen or for instance an alkoxy group,

similar dyestufis are obtained, the shades of which are more reddish or greenish respectively accord.- ing to the substituents.

We claim:

1. The dyestuffs of the thiazine series corre- [mm B.

spending to the general formula:

wherein R and'Rrindic'atean'arylj radicleof'the" '4'."Ihe dyestuif of'the thiazine' series'correbenzene, diphenyl or naphthalene series at least m-sM-nn-a-n H benzene, diphenyl or naphthalene series at least one a-ryl radicle signified by R and R1 belonging to the benzene series, X hydrogen or a methyl group and Y halogen;

3. The dyestufl of the thiazine series corresponding to the formula:

which dyestufi dissolves in concentrated sulur idw hfi u o rwh h y s fiv is easily soluble in the sodium sulfide bath and dyes cotton therefrom greenish blue shades of a par- ;ticular brightness and a good fastness.

r astee spending to the formula:

which dyestufi dissolves in concentrated sulfuric acid with a. blue, in warm nitrobenzene with a reddish blue coloration, which dyestufi is soluble in the sodium sulfide bath and dyes cotton therefrom greenish blue'shades of a particular brightness and of a good'fastness.

5. The dyestuif of the thiazine series corresponding to the formula:

wherein R and R1 indicate an aryl radicle of the which dyestufi dissolves in concentrated sulfuric acid and in nitrobenzene with a blue: coloration, which dyestufi is soluble in the sodium sulfide bath and dyes cotton therefrom greenish blue shades of a particular brightness and of a good DHERZ; V 4' '7 WERNER ZERWECK. 'WILHELMi-IECHTENBERG. 

